WO2021200779A1 - 電気化学デバイス - Google Patents

電気化学デバイス Download PDF

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WO2021200779A1
WO2021200779A1 PCT/JP2021/013179 JP2021013179W WO2021200779A1 WO 2021200779 A1 WO2021200779 A1 WO 2021200779A1 JP 2021013179 W JP2021013179 W JP 2021013179W WO 2021200779 A1 WO2021200779 A1 WO 2021200779A1
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positive electrode
negative electrode
electrochemical device
conductive agent
conductive
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English (en)
French (fr)
Japanese (ja)
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信敬 武田
卓也 廣部
良太 森岡
健一 永光
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Panasonic Intellectual Property Management Co Ltd
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Panasonic Intellectual Property Management Co Ltd
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Priority to CN202180023500.5A priority Critical patent/CN115315766A/zh
Priority to US17/905,645 priority patent/US20230129000A1/en
Priority to JP2022512181A priority patent/JPWO2021200779A1/ja
Publication of WO2021200779A1 publication Critical patent/WO2021200779A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This disclosure relates to electrochemical devices.
  • Patent Documents 1 and 2 An electrochemical device using polyaniline or the like as a positive electrode material can be charged and discharged by adsorption (doping) and desorption (dedoping) of anions.
  • Electrochemical devices used as power storage devices are required to have high capacity and low resistance.
  • One of the objects of the present disclosure is to provide an electrochemical device capable of increasing the capacity and reducing the resistance.
  • the electrochemical device is an electrochemical device including a positive electrode and a negative electrode, wherein the positive electrode contains a positive electrode material layer, and the positive electrode material layer contains particles of an active material and a conductive agent, and is of the active material.
  • the cohesive force between the particles and the conductive agent is larger than the cohesive force between the conductive agents.
  • an electrochemical device capable of increasing capacity and decreasing resistance can be obtained.
  • FIG. 1 is a cross-sectional view schematically showing an example of the electrochemical device of the present disclosure.
  • the first electrochemical device includes a positive electrode and a negative electrode.
  • the positive electrode includes a positive electrode material layer.
  • the positive electrode material layer contains particles of the active material and a conductive agent.
  • the cohesive force between the particles of the active material and the conductive agent is larger than the cohesive force between the conductive agents.
  • the conductive agent may be arranged on the surface of the particles of the active material.
  • the first electrochemical device can have a high capacity and a low resistance as described in Examples.
  • the particles of the active material and the conductive agent used for the positive electrode of the first electrochemical device are the same as the particles and the conductive agent of the conductive polymer used for the positive electrode of the second electrochemical device, respectively. Is omitted. Since the parts other than the positive electrode of the first electrochemical device are the same as the parts other than the positive electrode of the second electrochemical device, overlapping description will be omitted.
  • the second electrochemical device includes a positive electrode and a negative electrode.
  • the positive electrode includes a positive electrode material layer.
  • the positive electrode material layer contains particles of a conductive polymer, a dopant, and a particulate conductive agent.
  • the particles of the conductive polymer contained in the positive electrode material layer may be referred to as “conductive polymer (P)”.
  • the particulate conductive agent contained in the positive electrode material layer may be referred to as "conductive agent (C)” below.
  • the second electrochemical device satisfies the following configurations (1) to (3).
  • the average particle size of the conductive polymer (P) is in the range of 1 ⁇ m to 5 ⁇ m.
  • the average particle size of the conductive agent (C) is in the range of 5 nm to 30 nm.
  • the amount of DBP absorbed by the conductive agent (C) is in the range of 110 ml / 100 g to 160 ml / 100 g.
  • the average particle diameters of the conductive polymer (P) and the conductive agent (C) are median diameters (D 50 ) at which the cumulative volume is 50% in the volume-based particle size distribution, respectively.
  • the median diameter is determined using, for example, a laser diffraction / scattering particle size distribution measuring device.
  • the amount of DBP absorbed by the conductive agent (C) is a value measured according to JIS K6217-4 (2008).
  • the particles of the conductive polymer have a higher interfacial resistance than other materials such as activated carbon particles. Therefore, when the conductive polymer particles are used as the material responsible for charging and discharging in the positive electrode, the resistance is not sufficiently lowered by simply adding the conductive agent, unlike the case where the activated carbon particles and the like are used.
  • the conductive polymer constituting the conductive polymer (P) may be at least one selected from polyaniline and its derivatives.
  • the first and second electrochemical devices may include a positive electrode, a negative electrode, a separator, an electrolyte, and a case containing them, respectively.
  • the negative electrode, the separator, the electrolyte, and the case the negative electrode, the separator, the electrolyte, and the case used in the lithium ion secondary battery may be used. Examples of positive electrodes, negative electrodes, separators, and electrolytes will be described below.
  • the case is not particularly limited, and a case used for a lithium ion secondary battery or a case similar to a case used for an electric double layer capacitor may be used.
  • the positive electrode of the second electrochemical device will be described below.
  • the positive electrode may include a positive electrode core material, and the positive electrode material layer may be arranged on the positive electrode core material.
  • a ⁇ -conjugated polymer As the conductive polymer constituting the conductive polymer (P) used for the positive electrode material layer, a ⁇ -conjugated polymer is preferably used.
  • the ⁇ -conjugated polymer for example, polypyrrole, polythiophene, polyfuran, polyaniline, polythiophene vinylene, polypyridine, and derivatives thereof can be used. These may be used alone or in combination of two or more.
  • the weight average molecular weight of the conductive polymer is not particularly limited, and may be in the range of, for example, 1000 to 100,000.
  • the derivatives of polypyrrole, polythiophene, polyfuran, polyaniline, polythiophene vinylene, and polypyridine mean polymers having polypyrrole, polythiophene, polyfuran, polyaniline, polythiophene vinylene, and polypyridine as basic skeletons, respectively.
  • the dopant may be a polymer ion.
  • high molecular weight ions include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacrylic sulfonic acid, polymethacrylic sulfonic acid, poly (2-acrylamide-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and polyacrylic.
  • Examples include ions such as acid. These may be homopolymers or copolymers of two or more kinds of monomers. These may be used alone or in combination of two or more.
  • a particulate conductive agent containing a conductive carbon material for example, a particulate conductive agent composed of a conductive carbon material
  • a particulate conductive agent composed of a conductive carbon material examples include carbon black.
  • Examples of carbon black include acetylene black, ketjen black, furnace black and the like. Furnace black is preferable because it is easy to obtain those having different DBP absorption amounts.
  • the content of the conductive polymer (P) in the positive electrode material layer may be in the range of 60 to 90% by mass.
  • the content of the conductive agent (C) in the positive electrode material layer may be in the range of 1 to 20% by mass.
  • the thickness of the positive electrode material layer is not particularly limited, and may be in the range of, for example, 10 ⁇ m to 300 ⁇ m.
  • the positive electrode material layer may contain a substance other than the conductive polymer (P) and the conductive agent (C), if necessary.
  • the positive electrode material layer may contain a binder or the like.
  • the binder include fluororesin, acrylic resin, rubber material, cellulose derivative and the like.
  • the fluororesin include polyvinylidene fluoride, polytetrafluoroethylene, and tetrafluoroethylene-hexafluoropropylene copolymer.
  • the acrylic resin include polyacrylic acid and acrylic acid-methacrylic acid copolymers.
  • the rubber material include styrene-butadiene rubber.
  • the cellulose derivative include carboxymethyl cellulose.
  • the positive electrode material layer may be formed by applying a mixture (positive electrode mixture paste or dispersion liquid) containing a material constituting the positive electrode material layer and a dispersion medium to the positive electrode core material, and then drying the mixture.
  • the material constituting the positive electrode material layer contains a conductive polymer (P) and a conductive agent (C).
  • the dispersion medium water, a non-aqueous solvent such as alcohol, or a mixed solution thereof may be used.
  • the conductive polymer (P) in the positive electrode material layer may be formed by electrolytic polymerization.
  • the conductive polymer (P) may be formed by immersing the positive electrode core material in a reaction solution containing the raw material monomer of the conductive polymer and electrolytically polymerizing the raw material monomer in the presence of the positive electrode core material.
  • the positive electrode material layer containing the conductive polymer is formed so as to cover the positive electrode core material.
  • the thickness of the positive electrode material layer can be controlled by the electrolytic current density, the polymerization time, and the like.
  • chemical polymerization may be used instead of electrolytic polymerization.
  • the raw material monomer used in electrolytic polymerization or chemical polymerization may be any polymerizable compound capable of producing a conductive polymer by polymerization.
  • the raw material monomer may contain an oligomer.
  • As the raw material monomer for example, aniline, pyrrole, thiophene, furan, thiophene vinylene, pyridine or derivatives thereof are used. These may be used alone or in combination of two or more. Among them, aniline is likely to grow on the surface of the carbon layer by electrolytic polymerization.
  • Electrolytic polymerization or chemical polymerization may be carried out using a reaction solution containing an anion (dopant). By doping the ⁇ -electron conjugated polymer with a dopant, excellent conductivity is exhibited.
  • the positive electrode core material may be immersed in a reaction solution containing a dopant, an oxidizing agent, and a raw material monomer, and then withdrawn from the reaction solution and dried.
  • the positive electrode core material and the counter electrode may be immersed in a reaction solution containing a dopant and a raw material monomer, and a current may be passed between the positive electrode core material as an anode.
  • the positive electrode core material includes a positive electrode current collector.
  • a sheet-shaped metal material can be used for the positive electrode current collector. Examples of sheet-shaped metal materials include metal foils, porous metals, etched metals and the like. As the metal material, aluminum, aluminum alloy, nickel, titanium and the like may be used.
  • the thickness of the positive electrode current collector may be in the range of, for example, 10 ⁇ m to 100 ⁇ m.
  • the positive electrode core material may include a conductive layer (for example, a carbon layer) formed on the positive electrode current collector.
  • the conductive layer can improve the current collecting property from the positive electrode material layer to the positive electrode current collector.
  • the carbon layer may be formed by depositing a conductive carbon material on a positive electrode current collector.
  • the carbon layer may be formed by forming a coating film of a paste containing a conductive carbon material on the positive electrode current collector and then drying the coating film.
  • the paste may contain a conductive carbon material, a polymeric material, and water or an organic solvent.
  • the thickness of the carbon layer may be in the range of 1 ⁇ m to 20 ⁇ m.
  • Examples of conductive carbon materials include graphite, hard carbon, soft carbon, carbon black and the like. Carbon black can form a thin carbon layer with excellent conductivity.
  • Examples of the polymer material include fluororesin, acrylic resin, polyvinyl chloride, styrene-butadiene rubber (SBR) and the like.
  • the negative electrode includes a negative electrode material layer.
  • the negative electrode may include a negative electrode core material, and the negative electrode material layer may be arranged on the negative electrode core material.
  • the sheet-shaped metal material is used for the negative electrode core material.
  • the sheet-shaped metal material may be a metal foil, a metal porous body, an etched metal, or the like.
  • As the metal material copper, copper alloy, nickel, stainless steel and the like can be used.
  • the thickness of the negative electrode core material may be in the range of, for example, 10 to 100 ⁇ m.
  • the negative electrode material layer preferably includes, as the negative electrode active material, a material that electrochemically occludes and releases lithium ions.
  • examples of such materials include carbon materials, metal compounds, alloys, ceramic materials and the like.
  • the carbon material graphite, non-graphitized carbon (hard carbon), and easily graphitized carbon (soft carbon) are preferable, and graphite and hard carbon are particularly preferable.
  • the metal compound include silicon oxide and tin oxide.
  • Examples of the alloy include a silicon alloy and a tin alloy.
  • the ceramic material include lithium titanate and lithium manganate. These may be used alone or in combination of two or more.
  • the carbon material is preferable in that the potential of the negative electrode can be lowered.
  • the negative electrode material layer may contain a conductive agent, a binder, or the like in addition to the negative electrode active material.
  • the conductive agent include carbon black and carbon fiber.
  • the binder the binder exemplified as the binder that can be used for the positive electrode material layer may be used.
  • the negative electrode material layer may be manufactured by the same method as the method for manufacturing the negative electrode of the lithium ion secondary battery.
  • a negative electrode active material, a conductive agent, a binder, and the like are mixed together with a dispersion medium to prepare a negative electrode mixture paste, and the negative electrode mixture paste is applied to the negative electrode current collector. It is formed by drying.
  • the thickness of the negative electrode material layer may be in the range of, for example, 10 ⁇ m to 300 ⁇ m.
  • pre-doping lithium ions to the negative electrode first, a metallic lithium film serving as a lithium ion supply source is formed on the surface of the negative electrode material layer. Next, the negative electrode on which the metallic lithium film is formed is immersed in an electrolytic solution having lithium ion conductivity (for example, a non-aqueous electrolytic solution). As a result, pre-doping of lithium ions to the negative electrode proceeds. At this time, lithium ions are eluted from the metallic lithium film into the non-aqueous electrolytic solution, and the eluted lithium ions are occluded in the negative electrode active material.
  • an electrolytic solution having lithium ion conductivity for example, a non-aqueous electrolytic solution
  • lithium ions are inserted between the graphite layers and the pores of the hard carbon.
  • the amount of lithium ions to be pre-doped can be controlled by the mass of the metallic lithium film.
  • the amount of lithium ions pre-doped may be, for example, in the range of 50% to 95% of the maximum amount of lithium ions that can be occluded in the negative electrode material layer.
  • the step of predoping lithium ions on the negative electrode may be performed before assembling the electrode group.
  • the non-aqueous electrolyte solution and the electrode group may be housed in the container of the electrochemical device and then pre-doped.
  • a woven fabric made of an insulating material, a non-woven fabric, a porous film, or the like may be used.
  • a non-woven fabric made of cellulose fiber, a non-woven fabric made of glass fiber, a microporous film made of polyolefin, a woven fabric, a non-woven fabric, or the like may be used.
  • the thickness of the separator may be in the range of, for example, 10 ⁇ m to 300 ⁇ m (for example, 10 ⁇ m to 40 ⁇ m).
  • the separator is placed between the positive electrode and the negative electrode.
  • An electrode body is composed of a positive electrode, a negative electrode, and a separator.
  • the electrode body may be formed by winding a positive electrode, a negative electrode, and a separator.
  • the electrode body may be formed by laminating a positive electrode, a negative electrode, and a separator.
  • the electrolyte has lithium ion conductivity, contains a lithium salt and a solvent for dissolving the lithium salt, and has lithium ion conductivity.
  • the lithium salt anion may be one that reversibly repeats doping and dedoping of the positive electrode. Lithium ions derived from lithium salts are reversibly occluded and released to the negative electrode.
  • the electrolyte may be a non-aqueous electrolyte solution or a non-aqueous electrolyte solution used in a lithium ion secondary battery.
  • lithium salt examples include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiFSO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , LiCl, LiBr, LiI. , LiBCl 4 , LiN (FSO 2 ) 2 , LiN (CF 3 SO 2 ) 2, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, a salt having a fluorine-containing anion is preferable.
  • the concentration of the lithium salt in the non-aqueous electrolyte in the charged state may be, for example, 0.2 to 5 mol / L.
  • Solvents include cyclic carbonates such as ethylene carbonate, propylene carbonate and butylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and aliphatic carboxylics such as methyl formate, methyl acetate, methyl propionate and ethyl propionate.
  • Acid esters lactones such as ⁇ -butyrolactone and ⁇ -valerolactone, chain ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE) and ethoxymethoxyethane (EME), tetrahydrofuran , Cyclic ethers such as 2-methyl tetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acetonitrile, propionitrile, nitromethane, ethyl monoglyme, trimethoxymethane, sulfolane, methylsulfolane, 1, , 3-Propane salton, etc. can be used. These may be used alone or in combination of two or more.
  • the electrolyte may contain various additives, if necessary.
  • the electrolyte may include unsaturated carbonates such as vinylene carbonate, vinylethylene carbonate, and divinylethylene carbonate. These additives form a lithium ion conductive film on the surface of the negative electrode.
  • the positive electrode can be charged and discharged by doping and dedoping a dopant (for example, an anion) on the conductive polymer (P). Further, in the negative electrode, charging / discharging can be performed by occlusion and release of lithium ions.
  • a dopant for example, an anion
  • the first electrochemical device of the present disclosure can also have the same configuration as the electrochemical device illustrated below.
  • the above-mentioned components can be applied to the components of the electrochemical device described below.
  • the electrochemical device described below can be modified based on the above description.
  • the matters described below may be applied to the above-described embodiment.
  • components that are not essential to the electrochemical device of the present disclosure may be omitted.
  • FIG. 1 A cross-sectional view of the electrochemical device 200 of the first embodiment, which is an example of the second electrochemical device, is schematically shown in FIG. In FIG. 1, hatching of some members is omitted.
  • the electrochemical device 200 includes an electrode body 100, a non-aqueous electrolyte solution (not shown), a metal bottomed cell case (container) 210 accommodating the electrode body 100 and the non-aqueous electrolyte solution, and a cell case 210. Includes a sealing body 220 for sealing the opening of and a gasket 221.
  • the electrode body 100 is configured as a columnar winding body by, for example, winding a strip-shaped positive electrode 10 and a negative electrode 20 together with a separator 30 interposed between them.
  • the electrode body 100 may be configured as a laminated body in which a plate-shaped positive electrode and a negative electrode are laminated via a separator.
  • the positive electrode 10 includes a positive electrode core material and a positive electrode material layer supported on the positive electrode core material.
  • the negative electrode 20 includes a negative electrode core material and a negative electrode material layer supported on the negative electrode core material.
  • a gasket 221 is arranged on the peripheral edge of the sealing body 220.
  • the inside of the cell case 210 is sealed by crimping the open end of the cell case 210 to the gasket 221.
  • the positive electrode current collector plate 13 having the through hole 13h in the center is welded to the positive electrode core material exposed portion 11x.
  • One end of the tab lead 15 is connected to the positive electrode current collector plate 13, and the other end is connected to the sealing body 220. Therefore, the sealing body 220 has a function as a positive electrode terminal.
  • the negative electrode current collector plate 23 is welded to the negative electrode core material exposed portion 21x.
  • the negative electrode current collector plate 23 is welded to a welding member arranged on the bottom surface of the cell case 210. Therefore, the cell case 210 has a function as a negative electrode terminal.
  • the positive electrode 10 and the negative electrode 20 are manufactured by the method described above.
  • the positive electrode 10, the negative electrode 20, and the separator 30 are wound together to form the electrode body 100.
  • the positive electrode core material exposed portion 11x of the positive electrode 10 is connected to the positive electrode current collector plate 13.
  • the negative electrode core material exposed portion 21x of the negative electrode 20 is welded to the negative electrode current collector plate 23.
  • the electrode body 100 is housed in the cell case 210 together with the non-aqueous electrolytic solution (not shown).
  • the positive electrode current collector plate 13 and the sealing body 220 are connected by the tab lead 15, and the negative electrode current collector plate 23 and the cell case 210 are connected.
  • the sealing body 220 is arranged in the opening of the cell case 210, and the cell case 210 is sealed. Specifically, the vicinity of the open end of the cell case 210 is drawn inward. In this way, the electrochemical device 200 is obtained. As described above, pre-doping is performed at an appropriate stage as necessary.
  • the cylindrical winding type electrochemical device has been described, but the electrochemical device of the present disclosure may be another form of electrochemical device.
  • the electrochemical device of the present disclosure can also be applied to a square-shaped winding type electric device and a laminated type electrochemical device.
  • Example 1 In Example 1, first and second electrochemical devices were made and evaluated. In the production of the following devices, commercially available conductive polymers (P) having different average particle sizes and conductive agents (C) having different average particle sizes and DBP absorption amounts were used.
  • P conductive polymers
  • C conductive agents
  • the electrochemical device A1 was produced by the following method.
  • a mixture (positive electrode slurry) containing the material constituting the positive electrode material layer and the dispersion medium was prepared.
  • the conductive polymer (P) polyaniline particles having an average particle size (D 50 ) of 3 ⁇ m were used.
  • Carbon black was used as the conductive agent (C).
  • the carbon black one having an average particle size (D 50 ) of 5 nm and a DBP absorption amount of 160 ml / 100 g was used.
  • the mixture is a dispersion of a conductive polymer (P), a conductive agent (C), a dispersion of carboxymethyl cellulose (CMC), and a dispersion of styrene-butadiene rubber (SBR) at 100: 17.5: 3.0.
  • a coating film was formed by applying the above mixture (positive electrode slurry) to both sides of the positive electrode core material with a bar coater.
  • the core material on which the coating film was formed was heated to about 60 to 90 ° C. on a hot plate, and further vacuum dried at 110 ° C. for 12 hours.
  • the positive electrode was produced in this way.
  • a copper foil having a thickness of 20 ⁇ m was prepared as a negative electrode current collector. Further, a mixed powder obtained by mixing 97 parts by mass of hard carbon, 1 part by mass of carboxycellulose, and 2 parts by mass of styrene-butadiene rubber and water are kneaded at a mass ratio of 40:60 to obtain a negative electrode. A mixture paste was prepared. Next, the negative electrode mixture paste was applied to both sides of the negative electrode current collector and dried. In this way, a negative electrode having a negative electrode material layer having a thickness of 35 ⁇ m on both sides was obtained. Next, pre-doping with metallic lithium was performed. The amount of this metallic lithium was calculated so that the negative electrode potential in the electrolytic solution after the completion of pre-doping was 0.2 V or less with respect to metallic lithium.
  • the electrode After connecting the lead tabs to the positive electrode and the negative electrode, respectively, the electrode is wound by winding a laminate in which a cellulose non-woven fabric separator (thickness 35 ⁇ m), the positive electrode and the negative electrode are alternately laminated. Formed a group.
  • a solvent was prepared by adding 0.2% by mass of vinylene carbonate to a mixture of propylene carbonate and dimethyl carbonate in a volume ratio of 1: 1. By dissolving LiPF 6 at a predetermined concentration as a lithium salt to the resulting solvent, hexafluorophosphate ion as an anion - to prepare a nonaqueous electrolytic solution having a (PF 6).
  • Electrochemical devices A2-A7 and C1-C7 The electrochemical devices A2 to A2 to the same method as the electrochemical device A1 except that the average particle size of the conductive polymer (P), the average particle size of the conductive agent (C), and the amount of DBP absorbed were changed. A7 and C1 to C7 were prepared.
  • the average particle size of the conductive polymer (P) used in these electrochemical devices, and the average particle size and DBP absorption amount of the conductive agent (C) are shown in Table 1 below.
  • the capacitance density was measured by the following method. First, the produced electrochemical device was charged at 10 C to 3.6 V. After holding at 3.6 V for 10 minutes, the electrochemical device was left for 1 minute and then discharged at 10 C to 2.2 V, and the discharge capacity was measured. Then, the capacity density was determined by dividing the measured discharge capacity by the mass of the conductive polymer (P) in the positive electrode.
  • the internal DC resistance was measured by the following method. First, the prepared electrochemical device was charged at 3.6 V, 10 C (where C stands for C rate) for 10 minutes. After charging, the electrochemical device was left for 1 minute and then discharged at 10C. The voltage between the terminals of the electrochemical device in the section from 0.05 seconds to 0.2 seconds after the start of discharge was measured, and the amount of voltage drop was determined. Then, the internal DC resistance of the electrochemical device was calculated from the relationship between the voltage drop amount and the discharge current.
  • Table 1 shows the physical characteristics of the material used for producing the positive electrode of the above-mentioned electric device and the evaluation results of the above-mentioned electric device.
  • the average particle size ratio K / J shown in Table 1 is a value obtained by dividing the average particle size K of the conductive polymer (P) by the average particle size J of the conductive agent (C).
  • the average particle size of the conductive polymer (P) is in the range of 1 ⁇ m to 5 ⁇ m
  • the average particle size of the conductive agent (C) is in the range of 5 nm to 30 nm.
  • the DBP absorption amount of the conductive agent (C) was in the range of 110 ml / 100 g to 160 ml / 100 g, a high-capacity, low-resistance electrochemical device was obtained.
  • conductive polymer particles conductive polymer (P)
  • conductive polymer (P) As a material involved in charging / discharging, it is important that the conductive polymer (P) is covered with the conductive agent (C) as uniformly as possible. Is considered to be. For that purpose, it is necessary to suppress the aggregation of the conductive agents (C) with each other and increase the proportion of the conductive agent (C) present on the surface of the conductive polymer (P). It is considered that the proportion of the conductive agent (C) present on the surface of the conductive polymer (P) can be increased by satisfying the above conditions (1) to (3).
  • the cohesive force between the particles of the active material (conductive polymer (P)) and the conductive agent (C) is higher than the cohesive force between the conductive agents (C). Is also considered to be large.
  • the cohesive force between the particles of the active material (conductive polymer (P)) and the conductive agent (C) is considered to be smaller than the cohesive force between the conductive agents (C). ..
  • This disclosure can be used for power storage devices.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Citations (5)

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Publication number Priority date Publication date Assignee Title
JPH11162470A (ja) * 1997-11-25 1999-06-18 Toyo Alum Kk 集電体用アルミニウム箔とその製造方法、集電体、二次電池および電気二重層コンデンサ
JP2001126733A (ja) * 1999-10-27 2001-05-11 Sony Corp 非水電解質電池
JP2007103041A (ja) * 2005-09-30 2007-04-19 Dainippon Printing Co Ltd 非水電解液二次電池用電極板、及び非水電解液二次電池
JP2009253168A (ja) * 2008-04-09 2009-10-29 Nippon Zeon Co Ltd 電気化学素子電極の製造方法
WO2019208733A1 (ja) * 2018-04-26 2019-10-31 日東電工株式会社 蓄電デバイス用正極及び蓄電デバイス

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020072250A (ja) * 2018-04-26 2020-05-07 日東電工株式会社 蓄電デバイス用正極及び蓄電デバイス

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11162470A (ja) * 1997-11-25 1999-06-18 Toyo Alum Kk 集電体用アルミニウム箔とその製造方法、集電体、二次電池および電気二重層コンデンサ
JP2001126733A (ja) * 1999-10-27 2001-05-11 Sony Corp 非水電解質電池
JP2007103041A (ja) * 2005-09-30 2007-04-19 Dainippon Printing Co Ltd 非水電解液二次電池用電極板、及び非水電解液二次電池
JP2009253168A (ja) * 2008-04-09 2009-10-29 Nippon Zeon Co Ltd 電気化学素子電極の製造方法
WO2019208733A1 (ja) * 2018-04-26 2019-10-31 日東電工株式会社 蓄電デバイス用正極及び蓄電デバイス

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